Mono-azodyestuffs insoluble in water



Patented Mar. 22, 1938 UNITED STATES PATENT OFFICE MONO-AZODYE STUFFS INSOLUBLE IN WATER Ernst Fischer,

Offenbachon-the-Main,

Ger-

many, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No v Drawing.

Serial No. 101,887. 21, 1935 Claims.

The present invention relates to mono-azodyestuffs insoluble in water; more particularly it relates to dyestufis of the following general forwherein X1 stands for a member of the group consisting of hydrogen, alkyl, alkoxy and halogen, X2 and X3 stand for members of the group consisting of hydrogen, alkyl, alkoxy, halogen and the group -NH.CO.R.3, R3 being a member of the group consisting of alkyl, benzyl, a radical of the benzene and naphthalene series and a hydroaromatic radical, always one of the three substituents X1, X2 and IQ being an alkoxy group and always one of the two substituents X2 and X3 being the group NH.CO.R3, wherein Z stands.

for a member of the group consisting of hydrogen, halogen and alkoxy, Z being alkoxy in case X2 stands for the group NH.CO.R3 and one of the substituents X1 and X3 for a member of the group consisting of hydrogen and halogen.

I have found that valuable violet to blue monoazodyestufis are obtainable by combining the diazo-compounds from amines of the general'formula:

wherein X1 stands for hydrogen, alkyl, alkoxy or I ,I halogen, X2 and. X; stand for hydrogen, alkyl,

Application September 21, 1936,

In Germany September alkoxy, halogen or the group NH.CO.R3, R3 being alkyl, aryl, aralkyl or a hydroaromatic radical, always one of the three substituents X1, X2 and X2 being an alkoxy group and always one of the two substituents X2 and IQ being the group -NH.CO.R3, with arylides of Z-hydroxynaphthalene-B-carboxylic acid of the following general formula:

OH Y:

wherein the benzene radical It contains substituents in at least one of the two positions Y1 and Y2, such as alkyl, alkoxy, aryloxy groups or halogen, R1 and R2 stand for hydrogen, alkyl, aryl, aralkyl or hydroaromatic radicals and Z stands for hydrogen, halogen or alkoxy, Z being alkoxy in case X2 stands for the group -,Nl-I.CO.R3 and simultaneously X1 or X3 represent hydrogen or halogen, only such dyestufi components being used as do not contain any group imparting solubility, such as the sulfonic or carboxylic acid group. r

The dyestuffs can be produced in known manner on the fiber (native or regenerated cellulose), in substance or on a substratum. They may advantageously be used for the manufacture of very fast color lakes and for coloring cellulose esters and ethers, natural and artificial resins, high molecular, organic plastic masses as; 1 for instance, products made from nitro-cellulose,

resins prepared from formaldehyde and urea, phenols or amines, vinyl resins, natural rubber and the synthetic products which have a constitution and properties similar to those of natural rubber. The rubber dyeings thus obtained are of great technical value, since the new dyestuffs are insoluble in benzine, fast to vulcanization, very fast to light and do not bleed into white rubber during the vulcanization process. Especially with regard to the non-bleeding the present dyestuffs are distinctly superior to the comparable combinations, which are proposed for coloring plastic masses by German Patent No. 601,254.

The dyestuffs from naphthols in the R1 --B QzN group of which R1 and R2 represent alkyl, aryl, F

aralkyl or hydroaromatic radicals are much more adapted for the production of dyeings on the fiber (native and regenerated cellulose) than those wherein R1 or R2 or both stand for hydrogen.

The following examples serve to illustrate the invention, but they are not intended to limit it.

thereto:

(1) The goods which are impregnated with 6 grams per liter of the 2.3-hydroxynaphthoyl-1'- amino 4' methylbenzene sulfodiethylamide are developed in known manner with a neutralized diazo bath from 3 grams of 1-amino-2.5-diethoxy-4-benzoylaminobenzene per liter, rinsed and soaped. A reddish blue of good fastness properties is obtained. The dyestuff corresponds with the following formula:

By working in the same manner and using 2.3- hydroxynaphthoyl- 1 -amino -2 methylbenzene- 5-sulfodimethylamide as coupling component, a violet of similar properties is obtained.

(2) 15 grams of 1-amino-2.5-diethoxy4ben zoylaminobenzene are diazotized in the usual manner; Thereupon the diazo solution is mixed with sodium acetate in order to bind the excess of hydrochloric acid and then stirred into a solution of 19.2 grams of 2.3'-hydroxynaphthoyl-1'-amino- 4' methylbenzene 5' sulfoethylamide in dilute caustic soda solution. The separated dyestuff is filtered with suctiomwashed well and dried. It forms a blue violet powder. The lakes prepared therefrom in known manner possess good fastness properties. H, e

The combination may also be effected in the presence of a substratum adapted for the preparation of color lakes.

ample 2. 4 percent. of this dyestuff are incorporated with a suitable mixture of rubber, loading materials, sulfur and a vulcanization accelerator and the mixture is vulcanized in a vulcanization press for about 12 minutes at a steam pressure of 3 atmospheres above atmospheric pressure. There is obtained a blue violet vulcanizate which has a good fastness to light and neither bleeds into white rubber, nor gives rise to that phenomenon which is known as blushing or efliorescence when the rubber articles are stored.

(4) 13.6 grams of 1-amino-2.5-dimethoxy-4- benzoylaminobenzene are diazotized in the usual manner. The diazo solution which has been neutralized by means of sodium acetate until neutral to Congo paper is stirred into a solution of 21.4 grams of 2.3-hydroxynaphthoyl-1'-amino- 2-methoxybenzene-5-su1fodiethylamide in dilute caustic soda solution. The blue dyestuff' obtained is filtered with suction, washed well and dried. There is obtained a rubber product of a reddish blue shade which is fast to vulcanization and possesses very good fastness properties, when the mixture of rubber, the usual admixtures and 4 per cent. of the dyestufi is immersed into a solution of sulfur chloride in benzine and vulcanized in the cold.

(5) 23 grams of 2.3-hydroxynaphthoy1-1'- amino-2' -methylbenzene-5' -sulfo -N- methylbenzylamide are dissolved in water and the necessary quantity of caustic soda solution and reprecipitated with acetic acid, while well stirring. Into this suspension there is introduced, while stirring, a diazo solution prepared in the usual manner from 15 grams of 1-amino-2.5-diethoxy- 4 -benzoylaminobenzene while simultaneously adding such a quantity of sodium acetate as is necessary for binding the excess of mineral acid. When the combination is finished, the blue dyestuff is filtered with suction, washed well and dried. It may be used for coloring casein artificial horn in the following manner:

A mixture is prepared from 200 grams of rennet casein, 8 grams of zinc white and 1 gram of the dyestuff and hardened by treating it with formaldehyde. A greenish blue colored hornlike mass is obtained which possesses very good fastness properties.

The following table illustrates a series of other dyestuffs which may be prepared according to the present invention and are especially adapted (3) Apigment dye which is adapted for coloring for coloring high-molecular organic plastic rubber products is prepared as described in Exmasses:

Dyestufi [rom Diazo compound 01- Coupled with- Shade 3.3-hudrozunaphthoul-1-amin0- l-amino-2.5-diethoxy-4-benzoylaminobenzena-. 2-methylbeuzene-5-sulfodiethylemide Reddishblue. dn 2-methoxybenzene-5-sulfodiethylamide Blue.

2-ethoxybenzene-5'-sulfodiinethylamide. Violet. 2-phenoxybenzene-H-szilfodibthylamide Reddish blue. 2-cl1lorobenzene-5-su]fodiethylamide Do. 2-methylbenzene-5-sulfamide Blue. 2-methylbenzene-5-sulfo n butylamide Blue violet 2-methylbenzene-5 -sulfo-isobutylamid Violet. 2-methylbenzene-5-suliobenzylamide.. Blue. 2-metl1ylbenzene-5-sulfocyclohexylamide Do. 2'-methylbenzene-5-sulfoanilide Do. 2'-met(li1y1benzene-5-sulfo N-methyl-cyclohexyl- Do.

aim e. 2-metl1oxybenzene-5-su1fo-N-methylani.lide Do. Zhnethylbenzene-5-sulfodibenzylamide Do. 2-me%1ylbenzene-5-su1fo-N-benzyl-cyclohexyl- Do.

am e. H 2-methylbenzene-5-sulfo-N-benzylanilide Do. do 2'-methylbenzene-5-suliodiphenylamide Do. 18 i-amm0-2.4-d1methoxy-fi benzoylaminobenzenm- 2'-methy1benzene-S-sulfodiethylamlde.. Violet.

Dyestufi from' Diazo compound of-- Coupled with- Shade p I 2.d-huclrozynaphthoyL-I-amin0- 19 l-amino-2meth0xy4-acetaminobenzene. L-.- l 2-metl1oxybenzene-5-sulfo-N-methylani1ide. Violet. 20 1-amino-2.5-d1ethoxy-4-phenacetylaminobenzene. 2-methylbenzene-5-sulfo-N-methylanilide Blue. 21 l-immoaj-diethoxyi-(2-naphthoyl)-amino-: 2-methoxybenzene-5-sulfo-N-methylanilide. Violet.

enzene. 22 I-aBmiHo-Z.5-diethoxy-4-hexahydrobenzoylamino- 2-111ethylbenzene-5-sulfodiethylamide Reddishblue enzene. 23 1-aJmino2.5-diethoxy-4-(4-chlorobenzoyl)-amin0- 2-methy1benzene-5-sulio-N-methylanilide Blue.

enzene. P 24 l-amin'o-2.5-dimethoxy-4-(4-chlorobenzoyl)- 2-methoxybenzene-5 -sulfo-N-methylauilide. Blue. amlnobenzene. v Q 25 l-amino-ZlS-dimethoxy-el-(4-methoxybenzoyl)- 2-metl1ylbeuzeue-5-sulfo-N-methylanilide Reddish am nobenzene. blue. 26 1-aJmmo-2-methoxy-5-methyl-4-benzoylamino- 2-methylbenzene-5-sulfo-N-methylanilide Violet.

euzeue. v 27 1agmino-Z-methoxy-5-chloro-4-benzoylamino- 2-methylbenzene-5 sulfo-N-methylanilide Do.

enzene. l 1 28 l-amino-5-methoXy-4-benzoylamiuobenzone 2-,methy1benzene-5-sulfodiethylamide Do. 29 l-aJmmo-2-methyl-5-meth0Xy-4-benzoylamino- 2-methylbenzene-5-sulfodiethylamide Do.

enzene. r t 1 30 111mmo-2-chloro-5-methoxy-4-benzoylamino- 2-methylbenzene-5esulfodiethylamide Do.

enzene. l 31 1-amino-2.6-diethoxyl-benzoylaminobenzene 4-methylbenzene-5-sulfo-n-butylamide Do. 32 l-amino-Z.fi-dimethoxy-al-benzoylaminobenzene; 4-methy1beuzene-5=sulfobenzylamide. Blue Violet 33 4-methy1benzene-5-sulfanilide Violet. 34 4-methy1benzene-5-sulfodiethylamide Blue violet 35 4-methoxybenzene-5-su1fodiethylamide. Violet. 36 4-phenoxybenzene-5-sulfodiethylamide. Do. 37 2.4-d imethylbenzene-5-sulfodimethylamide. Blue violet 38 do 2-methoxy-4-chlorobe11zene 5- sulfodimethyl- Do.

amide. t V 7 6-bromo-Efl-hydroxy-naphthcol-famine- 39 l-amino-zfi-diethoxy i-benzoylamiuobenzene 2 -methoxybenzene-5 sulfcdiethylamide Do. 40 do 2methylbenzene-5-sulfodiethylamide Rglidish a no. 6-methoz11-2.3-hydroz11-naphthoyl-1 -amino- 41 l-amino-Z-ethoxy-5-benzoylamiuobenzene 2-methylbenzene-5-sulfodiethylamide Violet. 42 1-%miuo-2-methoxy-4-methyl-5-benzoylamino- 2-methoxybenzene-5-sulfodiethylamide Do.

enzene. 43 l-amino-4-methoxyJ-acetaminobenzene 2-methylbenzene-5-sulfcdiethylamide Do. 44 1-amino-2-methyl-4-methoxy-5-benzoyl-aminodo Do. benzene. 45 1-am no-2-methoxy4-acetaminobenzene l do Do. 46 1-an11no-2-methoxy-5gmethyl-4-benzoyl-aminodo Do.

benzene. a v 47 l-gmiuo-2-chloro-5-methoxy-4-benzoyl-amino- .do Blue. enzene. p v 48 l-amino-Z.5-diethoxy-l-benzoylaminobenzeue. -2-methoxybenzene-5-su1fodiethylam1de Blue violet. 49 1amino-2.5-diethoxyl-beuzoylaminobenzene 2-methylbenzene-5-sulfodiethylemide Blue. 1

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

I claim:

1. The water-insoluble mono-azodyestuifs of the following general formula:

z 0 ONE wherein the benzene radical a. is substituted in at least one of the two positions Y1 and Y2 by a member of the group consisting of alkyl, alkoxy,

phenoxy and halogen, R1 and R2 stand for members of the group consisting of hydrogen, alkyl,

aryl, benzyland hydroaromatic radicals and the, diazo radical D stands for compounds of the following formula:

wherein X1 stands for a member of the group consisting of hydrogen, alkyl, alkoxy and halogen, X2 and X3 stand for members of the group consisting of hydrogen, alkyl, alkoxy, halogen and the group: -NH.CO.R3, R3 being a member of the group consisting of alkyl, benzyl, a radical of the benzene and naphthalene series and a hydroaromatic radical, always one of the three substituents X1, X2 and X3 being an alkoxy group and always one of the two substituents X2 and X3 being the group -NI-I.CO.R3, wherein Z stands for a member of the group consisting of hydrogen, halogen and alkoxy, Z being alkoxy in case X2 stands for the group --NH.CO.R3 and one of the substituents X1 and X: for a member of the group consisting of hydrogen and halogen, yielding fast violet to blue lakes and, when mixed with rubber products, violet to blue colorations of very good fastness to light and to vulcanization.

2. The water-insoluble mono-azodyestufis of the following general formula:

stands for a member of the group consisting of hydrogen, alkyl, alkoxy and halogen, yielding fast violet to blue lakes and, when mixed with rubber products, voilet to blue colorations of very good fastness to light and to vulcanization.

3. The water-insoluble mono-azodyestufi of the following formula:

NH.c0.o,tn

/OC:HE

f I? S OzNIELCzH;

yielding fast bluish violet lakes and, when mixed with rubber products, bluish violet colorations of very good fastness to light and to vulcanization.

4. The water-insoluble mono-azodyestufi of the following formula:

NH-C0.06H6

If ?OQNH-CH,.OHLCHLCHI /OH /CH3 ooNn yielding fast violet lakes and, when mixed with rubber products, voilet colorations of very good fastness to light and to vulcanization.

5. The water-insoluble mono-azodyestuff of the following formula:

yielding fast blue lakes and, when mixed with rubber products, blue colorations of very good fastness to light and to vulcanization.

ERNST FISCHER. 

